EP3409643B1 - Aluminiumnitridpartikel - Google Patents

Aluminiumnitridpartikel Download PDF

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Publication number
EP3409643B1
EP3409643B1 EP17744468.4A EP17744468A EP3409643B1 EP 3409643 B1 EP3409643 B1 EP 3409643B1 EP 17744468 A EP17744468 A EP 17744468A EP 3409643 B1 EP3409643 B1 EP 3409643B1
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Prior art keywords
aluminum nitride
particle
powder
resin
nitridation
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French (fr)
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EP3409643A1 (de
EP3409643A4 (de
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Akimasa KURAMOTO
Kikuo Yamamoto
Mou OU
Saiko FUJII
Yukihiro Kanechika
Teruhiko Nawata
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Tokuyama Corp
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Tokuyama Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/072—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with aluminium
    • C01B21/0726—Preparation by carboreductive nitridation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/072—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/282—Binary compounds of nitrogen with aluminium

Definitions

  • the present invention relates to an aluminum nitride particle having a novel form, an aluminum nitride powder containing the same and a production method of the same.
  • aluminum nitride Since aluminum nitride has high heat conductivity and excellent electric insulation, it is used as an insulation heat radiation filler to be filled into a heat radiation member.
  • a spherical filler having a large particle diameter and a spherical filler having a small particle diameter are used in combination and densely filled into a heat radiation member to increase the chances of contact between the fillers.
  • the particle diameter of aluminum nitride required as the above filler having a large particle diameter is 10 ⁇ m or more.
  • a mixture of an alumina powder, a carbon powder and a co-fusion agent is baked in the atmosphere of a mixed gas of nitrogen and carbon monoxide to reduce and nitride the above alumina powder ( WO2013/146894 ).
  • a mixed gas of nitrogen and carbon monoxide to reduce and nitride the above alumina powder
  • yttrium oxide, lithium oxide, cesium oxide and calcium oxide are used.
  • aluminum nitride having a particle diameter of 10 ⁇ m or more for example, there is known a method in which, after a sintering aid, an organic binder and a solvent are added to and mixed with an aluminum nitride powder, a spherical granulated power obtained by drying and granulating the resulting mixture is sintered ( JP-A 3-295863 ).
  • Aluminum nitride obtained by this method is spherical and has a particle diameter of about 80 ⁇ m.
  • aluminum nitride obtained by this method may have large voids therein due to the difference in drying rate between the inside and the outside of the above spherical granulated powder.
  • aluminum nitride particles are bonded together by sintering to form a polycrystal structure, whereby many fine irregularities are formed on the surfaces of the aluminum nitride particles after sintering. Therefore, when the above aluminum nitride particles are filled into a resin to obtain a molded body by using the obtained aluminum nitride particles and the resin, air bubbles are apt to remain at the interface between the above aluminum nitride particle and the resin in addition to the existence of the above voids, whereby the molded body obtained by molding a resin composition comprising the above aluminum nitride particles and the resin has a problem such as the deterioration of insulation resistance.
  • US 2015/353355 A1 describes aluminum nitride crystal particles, aluminum nitride powders containing the same, production processes for both of them, an organic polymer composition comprising the aluminum nitride crystal particles and a sintered body.
  • Each of the aluminum nitride crystal particles has a flat octahedral shape in a direction where hexagonal faces are opposed to each other, which is composed of two opposed hexagonal faces and 6 rectangular faces, in which the average distance "D" between two opposed corners of each of the hexagonal faces is 3 to 110 ⁇ m, the length "L” of the short side of each of the rectangular faces is 2 to 45 ⁇ m, and L/D is 0.05 to 0.8; each of the hexagonal faces and each of the rectangular faces cross each other to form a curve without forming a single ridge; and the true destiny is 3.20 to 3.26 g/cm 3 .
  • US 2015/376009 A1 describes a method for producing sintered aluminum nitride granules which includes a reduction nitridation step of carrying out the reduction nitridation of porous alumina granules at a temperature of 1400 to 1700° C inclusive to produce porous aluminum nitride granules; and a sintering step of sintering the porous aluminum nitride granules, which are produced in the reduction nitridation step, at a temperature of 1580 to 1900° C inclusive.
  • Lishan Yang, et al. (Dalton Transactions, vol. 39 (2010), pages 2855-2860 ) describe the sulfur-assisted synthesis of nitride nanocrystals.
  • JP H05 139709 A relates to the problem to obtain powdery nitride, having a very low degree of aggregation of primary particles and hardly causing shrinkage by sintering.
  • the document describes a powdery aluminum nitride which has an average particle diameter (D1) calculated from the specific surface area of 0.2-1.5 ⁇ m, preferably 0.3-1.0 ⁇ m, and a ratio of the average particle diameter (D2) measured by a sedimentation method to the average particle diameter (D1) of ⁇ 2.00, preferably ⁇ 1.95.
  • the inventors of the present invention conducted intensive studies to attain the above object and found that aluminum nitride obtained by the Carbo-thermal reduction-nitridation of a raw material mixture containing an alumina powder, a carbon powder and a specific amount of a sulfur component can be grown big without producing voids therein by controlling a reaction atmosphere to specific gas composition at least in the first half of a Carbo-thermal reduction-nitridation reaction, an aluminum nitride particle having such a characteristic form not existent in the prior art that it has a hexagonal columnar barrel part and bowl-like projection parts at both ends of the columnar part is obtained, and the aluminum nitride particle exhibits excellent heat conductivity as compared with conventional spherical particles when it is filled into a resin.
  • the present invention was accomplished based on this finding.
  • the present invention is an aluminum nitride particle having a hexagonal columnar barrel part and bowl-like projection parts at both ends of the columnar part, wherein the long diameter (D) of the above barrel part is 10 to 250 ⁇ m, the ratio (L 1 /D) of the distance (L 1 ) between the apexes of the above two projection parts to the long diameter (D) of the above barrel part is 0.7 to 1.3, and the percentage of the length or thickness (L 2 ) of the above barrel part to the distance (L 1 ) between the apexes of the above two projection parts is 10 to 60 %.
  • part of one or both of the two projection parts of the above aluminum nitride particle should be a flat surface, and it is more preferred that the flat surface should be polygonal.
  • the number of voids which have a diameter of 2 ⁇ m or more and are existent in the above aluminum nitride particle, is preferably 5 or less for each particle.
  • the aluminum nitride particle of the present invention is obtained as an aluminum nitride powder containing not less than 40 vol% of aluminum nitride particles having other forms such as indeterminate and spherical forms by a production method which will be described hereinafter. Even in the above aluminum nitride powder, the effect of the aluminum nitride particle of the present invention can be fully obtained.
  • a resin composition comprising the above aluminum nitride particle and a resin and a molded body formed from the resin composition.
  • the present invention also provides a preferred method of producing the above aluminum nitride powder. That is, according to the present invention, in a method of producing an aluminum nitride powder comprising heating a raw material mixture containing an alumina powder, a carbon powder and a sulfur component in a nitrogen gas atmosphere to reduce and nitride the alumina powder, in a nitridation rate of at least 3 to 50 %, the above Carbo-thermal reduction-nitridation is carried out by using a mixed gas of 85 to 55 vol% of a nitrogen gas and 15 to 45 vol% of a diluting gas as the above nitrogen gas atmosphere, and after the end of the Carbo-thermal reduction-nitridation, a temperature which is the heating temperature for the Carbo-thermal reduction-nitridation ⁇ 30°C is kept for 10 hours or more in an atmosphere in which the formed aluminum nitride powder is not oxidized.
  • the amount of the above sulfur component is suitably 1.0 to 20 parts by weight based on 100 parts by weight of the alumina powder.
  • the aluminum nitride particle 1 of the present invention has a hexagonal columnar barrel part 2 and bowl-like projection parts 3 and 3' at both ends of the columnar part.
  • hexagonal columnar means that the particle has a hexagonal columnar form.
  • the hexagonal column is preferably such that the hexagonal planes are regular hexagonal or that the six angles of the regular hexagon are 120 ⁇ 20°.
  • the two hexagonal columnar planes of the hexagonal column may be the same or different. Further, the hexagons of the two hexagonal columnar planes may have the same or different areas. When they have different areas, it is desired that the maximum area difference should be 10 %.
  • the hexagonal columnar barrel part is composed of six squares and/or rectangles defining the two hexagonal columnar planes and the hexagonal column.
  • the six squares and/or rectangles are preferably adjacent rectangles interconnected at short sides.
  • the length of each side of each of the rectangles changes depending on the above hexagons of the two hexagonal columnar planes.
  • the thickness (L 2 ) of the barrel part corresponding to the length of each of the short sides of the rectangle is about 0.7 to 195 pm, preferably 1 to 100 ⁇ m, more preferably 3 to 50 ⁇ m. When the lengths of the short sides of the rectangles of one particle are different, the above L 2 value is understood as average value.
  • the form of the above barrel part is not particularly limited if it is hexagonal columnar. Stated more specifically, although it is most preferred that the particle should be perfectly hexagonal columnar, corner parts are curved or chamfered flat, or part of the barrel part is depressed or projected as long as at least some of the flat faces of the hexagonal column are maintained. It is preferred that the barrel part should be almost perfectly hexagonal columnar as the contact area between the above aluminum nitride particles in the resin can be made large.
  • Fig. 3 is a schematic diagram of another example of the aluminum nitride particle of the present invention.
  • the columnar barrel faces are almost flat and it is understood from the plan view (b) that the column is hexagonal defined by six rectangles which are almost flat faces forming the barrel faces.
  • Fig. 4 is a schematic diagram of still another embodiment of the aluminum nitride particle of the present invention.
  • the columnar barrel faces are not flat and a part near the center part in the columnar direction is depressed from the flat faces and it is understood from the plan view (b) that the column is hexagonal defined by six rectangles defining the bottom faces of the projection parts in contact with the barrel part.
  • Fig. 5 is a schematic diagram of a further embodiment of the aluminum nitride particle of the present invention.
  • the columnar barrel faces are formed almost flat and it is understood from the plan view (b) that the column is hexagonal defined by rectangles forming the barrel faces and the projection part has a flat part at the center.
  • the other projection part which is not shown in the plan view (b) has a flat part at the center as well.
  • Fig. 6 is a schematic diagram of a still further embodiment of the aluminum nitride particle of the present invention.
  • the barrel faces of the column are formed almost flat and it is understood from the plan view (b) that the column is hexagonal defined by rectangles forming the barrel faces and the projection parts have a flat part at the center and are raised toward the flat parts along the hexagonal form of the barrel part.
  • the size of the projection part is smaller than the long diameter of the barrel part.
  • each of the above projection parts may be conical, dome-like or truncated pyramid-like and is not particularly limited but preferably part of the projection part is preferably flat, thereby making it possible to increase the contact area between the aluminum nitride particles advantageously.
  • the aluminum nitride particle of the present invention is further specified as follows. That is, the long diameter (D) of the above barrel part is 10 to 250 ⁇ m, preferably 10 to 100 ⁇ m, particularly preferably 20 to 80 ⁇ m. Further, the ratio (L 1 /D) of the distance (L 1 ) between the apexes of the above two projection parts 3 and 3' to the long diameter (D) of the above barrel part is 0.7 to 1.3, preferably 0.8 to 1.1, and the percentage of the length or thickness (L 2 ) of the barrel part to the distance (L 1 ) between the apexes of the above two projection parts is 10 to 60 %, preferably 20 to 60 %, particularly preferably 25 to 45 %.
  • the long diameter (D) of the barrel part is the largest one of three distances, each between two opposed corners of the hexagonal columnar plane.
  • the above aluminum nitride particle has a long diameter and a short diameter close to those of a sphere as understood from the fact that the L 1 /D is 0.7 to 1.3, when the aluminum nitride particle is filled into the resin, it has low orientation and can exhibit stable heat conductivity.
  • each of the above projection parts may be larger or smaller than the long diameter of the above barrel part.
  • the ratio of the long diameter of the projection part to the long diameter of the above barrel part is preferably 0.8 to 1.2, particularly preferably 0.9 to 1.1 so that the above aluminum nitride particle can have a form close to a preferred spherical form.
  • the aluminum nitride particle having the above characteristic form is provided by the present invention for the first time and has excellent heat conductivity which cannot be attained by a conventional spherical aluminum nitride particle in a resin due to its form.
  • the number of voids in the particle is small which is one of the characteristics of the aluminum nitride particle. Stated more specifically, the number of voids having a diameter of 2 ⁇ m or more in the above aluminum nitride particle is preferably 5 or less, particularly preferably 3 or less for each particle.
  • the aluminum nitride particle of the present invention can be obtained by a production method which will be described hereinafter. Since aluminum nitride except for the above aluminum nitride particle is partially produced, an aluminum nitride powder containing the aluminum nitride particle is generally obtained. Since the aluminum nitride powder of the present invention exhibits the above characteristic properties of the above aluminum nitride particle fully, it contains not less than 40 vol%, preferably not less than 60 vol% of the above aluminum nitride particle.
  • aluminum nitride except for the above aluminum nitride particle can be removed and separated from the above aluminum nitride powder with known classification means, for example, classification means using a sieve to increase the content of the above aluminum nitride particle.
  • the aluminum nitride particle of the present invention is not limited to particular use purposes and can be used for known purposes without restriction.
  • Examples of the preferred use of the aluminum nitride particle include use as a filler in a resin to improve electric insulation and provide heat conductivity.
  • a resin composition comprising the aluminum nitride particle and a resin and a molded body obtained by molding the resin composition have high electric insulation and high heat conductivity.
  • thermoplastic resins such as polyolefins, vinyl chloride resin, methyl methacrylate resin, nylon resin and fluororesin, thermosetting resins such as epoxy resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin and silicon resin, and synthetic rubbers.
  • the resin composition of the present invention is obtained by mixing the above aluminum nitride powder with the resin uniformly by means of a known mixer according to the type of the above resin to disperse the aluminum nitride particles in the resin.
  • a known mixer for example, ordinary kneading machines such as roll, kneader, Banbury mixer, and revolving and rotational mixers are preferably used.
  • the amount of the aluminum nitride particle is determined in consideration of the dispersibility of the aluminum nitride particle and the heat conductivity and moldability of the obtained molded body.
  • the aluminum nitride particle is used in an amount of preferably 300 to 1,000 parts by weight, more preferably 400 to 800 parts by weight based on 100 parts by weight of the resin.
  • the resin composition of the present invention may comprise components except for the above aluminum nitride particle and the resin as long as the excellent effect of the present invention is not greatly impaired.
  • one or more fillers such as aluminum nitride except for the above aluminum nitride particle, alumina, boron nitride, zinc oxide, silicon nitride, silicon carbide and graphite may be filled.
  • the forms and average particle diameters of the aluminum nitride particles of the present invention and a filler except for the aluminum nitride particles can be selected.
  • the molded body of the present invention can be obtained when the above thermoplastic resin or thermosetting resin is used as the resin.
  • the molding method for molding the molded body of the present invention is not particularly limited, conventionally known molding methods such as injection molding, transfer molding, extrusion molding, bulk molding, compound molding, compression molding and casting using a solvent may be used according to the type of the resin.
  • the form of the molded body of the present invention is not particularly limited as long as the effect of the present inventio is not greatly impaired. It may be sheet-like, film-like, disk-like or rectangular.
  • nitridation is carried out at a nitridation rate of at least 3 to 50 % in the presence of a mixed gas of 85 to 55 vol% of a nitrogen gas and 15 to 45 vol% of a diluting gas, and a temperature of (the heating temperature for Carbo-thermal reduction-nitridation ⁇ 30°C) is kept for 10 hours or more in an atmosphere in which the formed aluminum nitride powder is not oxidized after the end of Carbo-thermal reduction-nitridation.
  • alumina powder which is one of the above raw materials
  • known alumina such as ⁇ -alumina and ⁇ -alumina may be used.
  • ⁇ -alumina is particularly preferably used.
  • the purity of ⁇ -alumina is preferably not less than 99.0 wt%, more preferably not less than 99.5 wt%.
  • the average particle diameter of ⁇ -alumina is preferably 0.5 to 50 ⁇ m, more preferably 1 to 30 ⁇ m.
  • the carbon powder used as a reducing agent known carbon such as furnace black, channel black, thermal black and acetylene black may be used.
  • the average particle diameter of the carbon powder is preferably not more than 100 nm, more preferably not more than 50 nm.
  • the DBP oil absorption of the carbon powder is preferably 50 to 150 cm 3 /100 g, more preferably 70 to 130 cm 3 /100 g.
  • synthetic resin condensates such as phenol resin, melamine resin and epoxy resin condensates, hydrocarbon compounds such as pitch and tar, and organic compounds such as cellulose, sucrose, starch, polyvinylidene chloride and polyphenylene may be used as carbon sources as long as the effect of the present invention is not impaired.
  • the sulfur component is an essential component for the production of the aluminum nitride particle of the present invention which functions at the time of adjusting an atmosphere for a Carbo-thermal reduction-nitridation reaction which will be detailed hereinafter.
  • the type of the sulfur component is not particularly limited if it can co-melt with the alumina powder as a raw material.
  • sulfur alone and sulfur compounds such as aluminum sulfide, nitrogen sulfide and thiouric acid may be used.
  • the above sulfur components may be used alone or in combination.
  • a sulfur component may be contained in the carbon powder and serve as part of the sulfur component of the present invention.
  • the amount of the carbon powder is preferably 36 to 200 parts by weight, more preferably 40 to 100 parts by weight based on 100 parts by weight of the alumina powder.
  • the amount of the sulfur component contained in the raw material mixture containing the alumina powder and the carbon powder is preferably 1.0 to 20 parts by weight as elemental sulfur based on 100 parts by weight of the alumina powder. Since the volatilized sulfur may corrode the internal wall of a Carbo-thermal reduction-nitridation reaction furnace, the amount of the above sulfur component is preferably small, more preferably 2.5 to 10 parts by weight. The above range of the amount of the sulfur component can be satisfied by considering and adjusting the amount of sulfur contained in the carbon fiber and the amount of the sulfur powder and/or the sulfur compound to be added to the raw material mixture.
  • the amount of the carbon powder may be adjusted to achieve the above range, or a carbon powder having a high content of sulfur and a carbon powder having a low content of sulfur are used to achieve the above range by adjusting the mixing ratio of these.
  • any means is acceptable if it is capable of mixing together the raw materials uniformly.
  • a mixer such as a vibration mill, bead mill, ball mill, Henschel mixer, drum mixer, vibration agitator or twin-cylinder mixer may be used.
  • the method of producing the aluminum nitride powder of the present invention is a method in which the Carbo-thermal reduction-nitridation of an alumina powder is carried out by heating a raw material mixture containing the above alumina powder, carbon powder and sulfur component in a nitrogen gas atmosphere, wherein Carbo-thermal reduction-nitridation is carried out at a nitridation rate of at least 3 to 50 % in a mixed gas of 85 to 55 vol% of a nitriding gas and 15 to 45 vol% of a diluting gas as the above nitrogen gas atmosphere, and a temperature of (the heating temperature for Carbo-thermal reduction-nitridation ⁇ 30°C) is kept for 10 hours or more in an atmosphere in which the formed aluminum nitride powder is not oxidized after the end of Carbo-thermal reduction-nitridation.
  • a temperature at which the Carbo-thermal reduction-nitridation reaction proceeds is used as the above heating temperature, for example, preferably 1,500 to 2,000°C.
  • the above diluting gas is made existent in the atmosphere to adjust the ratio of the nitrogen gas in the nitrogen gas atmosphere and contains a carbon monoxide gas generated from the raw material mixture.
  • the type of the above diluting gas is preferably carbon monoxide alone or a mixed gas of carbon monoxide and an inert gas such as argon.
  • the Carbo-thermal reduction-nitridation reaction is preferably carried out while a nitrogen gas is let flow into a reactor containing the raw material mixture.
  • the ratio of the diluting gas in the nitrogen gas atmosphere in which the raw material mixture is existent can be checked by measuring the gas composition of an exhaust gas from the reactor.
  • the nitridation rate of the alumina powder as a raw material can be confirmed by sampling a reaction product in the reactor.
  • a Carbo-thermal reduction-nitridation reaction under the same conditions is stopped at a predetermined time and a reaction product is taken out to measure the nitridation rate, thereby making it possible to confirm the nitridation rate in the reaction.
  • the Carbo-thermal reduction-nitridation reaction is suppressed excessively, whereby the Carbo-thermal reduction-nitridation reaction takes a long time, which is industrially disadvantageous, and hexagonal columnar aluminum nitride having no projection parts is obtained or an unreacted alumina powder remains very often.
  • a mixed gas is prepared by mixing a predetermined amount of a diluting gas prepared separately with a nitrogen gas and supplied into a reactor in which the raw material mixture is contained in a carbon vessel with an open top, so-called "setter"
  • a method in which a mixture of the alumina powder and the carbon powder is placed at an upstream side of the raw material mixture in a flow of a nitrogen gas flowing in the reactor and the concentration of a carbon monoxide gas contained in a nitrogen gas to be supplied to the raw material mixture is adjusted with carbon monoxide produced by the Carbo-thermal reduction-nitridation of the mixture and (3) a method in which the raw material mixture is contained in the above setter to form a relatively thick layer, a nitrogen gas is supplied into the setter, and the amount of the nitrogen gas diffused into the inside of the above layer is controlled to form an atmosphere in which the ratio of a carbon
  • the ratio of the diluting gas in the nitrogen gas atmosphere in the reactor is adjusted in consideration of the amount of a carbon monoxide gas generated from the raw material mixture.
  • the amount of the mixture of the alumina powder and the carbon powder situated at an upstream side of the raw material mixture is determined to satisfy the above concentration by checking variations in the amount of the generated carbon monoxide gas in advance.
  • the above amount of the mixture of the alumina powder and the carbon powder which has been prepared within the range of the ratio of the alumina powder and the carbon powder is 0.7 to 1.3 times the amount of the raw material mixture based on the alumina powder.
  • a case in which the supply of the carbon monoxide gas becomes insufficient and the ratio of the carbon monoxide gas becomes lower than 15 vol% may occur temporarily in the initial stage of the Carbo-thermal reduction-nitridation reaction.
  • the above state is allowed until the nitridation rate becomes 3 %, preferably 5 %.
  • the lower limit of the range of the nitridation rate at which 15 to 45 vol% of a carbon monoxide gas is existent in a nitrogen gas can be made 3 %.
  • the above ratio of the carbon monoxide gas should be kept from the beginning of the Carbo-thermal reduction-nitridation reaction.
  • the thickness of the raw material mixture in the setter should be not smaller than 50 mm, specifically not smaller than 70 mm in order to adjust the ratio of the diluting gas to the above range when a nitrogen gas enters a space in the setter to promote Carbo-thermal reduction-nitridation.
  • the upper limit of the thickness is preferably not more than 200 mm, particularly preferably not more than 150 mm.
  • the supply of the diluting gas may be stopped or made small, thereby making it possible to reduce the ratio of the diluting gas to less than 15 vol%, or nitridation may be terminated under the same conditions.
  • the above retention time is preferably not longer than 50 hours, particularly preferably not longer than 30 hours.
  • the Carbo-thermal reduction-nitridation step of the present invention may be carried out by using a known apparatus capable of controlling a reaction atmosphere.
  • a known apparatus capable of controlling a reaction atmosphere.
  • an atmosphere control type high-temperature furnace in which high-frequency induction heating or heating with a heater is carried out is used.
  • a continuous nitridation reaction furnace such as a batch furnace, pusher type tunnel furnace or vertical furnace may also be used.
  • the excessive carbon powder is preferably removed by oxidation as required.
  • an oxidizing gas for oxidation a gas capable of removing carbon, such as air, oxygen or carbon dioxide, may be used without restriction.
  • the oxidizing temperature is preferably 500 to 900°C.
  • Alumina powder ⁇ -alumina average particle diameter of 1.183 ⁇ m * carbon powder Carbon powder A: average particle diameter of 19 nm, DBP absorption of 116 cm 3 /100 g, sulfur content of 210 ppm Carbon powder B: average particle diameter of 20 nm, DBP absorption of 115 cm 3 /100 g, sulfur content of 3,000 ppm * sulfur component sulfur powder: purity of not less than 98 %
  • the aluminum nitride particle of the present invention was selected from an image observed through a 2,000-power or 100-power SEM (TM3030 of Hitachi High-Technologies Corporation) to measure the diameter (D) of the barrel part, the distance (L 1 ) between the apexes of the projection parts and the length (L 2 ) of the barrel part of the aluminum nitride particle.
  • the ratio (L 1 /D) of the distance (L 1 ) between the apexes of the projection parts to the diameter (D) of the barrel part and the percentage of the length (L 2 ) of the barrel part to the distance (L 1 ) between the apexes of the projection parts were calculated.
  • the above aluminum nitride particles and other aluminum nitride particles were selected from the observation image of the 2,000-power or 100-power SEM to approximate all the above aluminum nitride particles and the other particles to a sphere, and the total volume of the above aluminum nitride particles in the field of view was obtained from the measurement value of the diameter (D) of the barrel part to obtain the vol% of the above aluminum nitride particle based on the volume of the aluminum nitride powder containing the above aluminum nitride particles and the other particles.
  • the aluminum nitride powder containing the above aluminum nitride particles was filled into an epoxy resin which was then cast into a mold and cured by a thermal press device to produce a sheet having a thickness of 100 ⁇ m.
  • a cross-section observation sample in the thickness direction of the above sheet was prepared from the sheet by a cross-section processing machine to select 5 aluminum nitride particles at random from a 2, 000-power or 100-power SEM observation image and count the number of voids having a diameter of not less than 2 ⁇ m. The average number of voids per each particle is given.
  • a test sample was molded from the resin composition to obtain heat conductivity from thermal diffusion factor, density and specific heat based on the following equation.
  • Heat conductivity thermal diffusion factor x density x specific heat
  • the thermal diffusion factor was measured by a laser flash method, the density was measured by an Archimedes method, and the specific heat was measured by DSC.
  • BDV breakdown voltage
  • a sulfur powder was added to a mixture of 100 parts by weight of an alumina powder and 50 parts by weight of a carbon powder to ensure that the amount of a sulfur component in the mixture became 2.5 parts by weight based on 100 parts by weight of the above alumina powder and mixed with the mixture by means of a vibration agitator until they were mixed together uniformly to obtain a raw material mixture.
  • the above raw material mixture was put into a carbon setter to a thickness of 50 mm, the setter was set in a reactor through which nitrogen could flow, and Carbo-thermal reduction-nitridation was carried out at a heating temperature of 1,750°C while a nitrogen gas was let flow.
  • a carbon monoxide gas was mixed with the nitrogen gas which was let flow through the above reactor to ensure that the proportion of the carbon monoxide gas of an exhaust gas from the reactor became 23 vol%.
  • the above reaction product was heated at 700°C for 5 hours in the atmosphere to burn and remove an unreacted carbon powder so as to obtain an aluminum nitride powder.
  • the proportion of the aluminum nitride particles having the characteristic form of the present invention contained in the obtained aluminum nitride powder was 90 vol%.
  • the particle diameters of the aluminum nitride particles were measured by the above measurement method for the particle diameters of aluminum nitride particles to calculate the average particle diameter of the above aluminum nitride particles.
  • Aluminum nitride particles (particles A, B and C) having a typical size and a typical form were selected from the aluminum nitride particles to measure their particle diameters. The results are shown in Table 2.
  • Example 2 An aluminum nitride powder was obtained in the same manner as in Example 1 except that the raw material composition in Example 1 was changed as shown in Table 1. The particle diameters and proportion of aluminum nitride particles contained in the obtained aluminum nitride powder and voids existent in each aluminum nitride particle were measured by the above methods. The results are shown in Table 2. An SEM Photo of the aluminum nitride particles obtained in this example is shown in Fig. 2 .
  • Example 2 An aluminum nitride powder was obtained in the same manner as in Example 1 except that the raw material composition in Example 1 was changed as shown in Table 1. The particle diameters and proportion of aluminum nitride particles contained in the obtained aluminum nitride powder and voids existent in each aluminum nitride particle were measured by the above methods. The results are shown in Table 2.
  • Example 2 An aluminum nitride powder was obtained in the same manner as in Example 1 except that the raw material composition in Example 1 was changed as shown in Table 1. The particle diameters and proportion of aluminum nitride particles contained in the obtained aluminum nitride powder and voids existent in each aluminum nitride particle were measured by the above methods. The results are shown in Table 2.
  • Example 2 An aluminum nitride powder was obtained in the same manner as in Example 1 except that the raw material composition in Example 1 was changed as shown in Table 1. The particle diameters and proportion of aluminum nitride particles contained in the obtained aluminum nitride powder and voids existent in each aluminum nitride particle were measured by the above methods. The results are shown in Table 2.
  • a molded body was produced by using an aluminum nitride powder containing the above aluminum nitride particles as a filler and an epoxy resin as a resin.
  • a mixture of 100 parts by weight of an epoxy resin (jER828 of Mitsubishi Chemical Corporation) as the resin and 5 parts by weight of a curing agent (imidazole-based curing agent, Cure Sol 2E4MZ of Shikoku Chemicals Corporation) was prepared. Then, 633 parts by weight of an aluminum nitride powder containing 70 vol% of aluminum nitride particles having an average particle diameter of 22 ⁇ m obtained by the production method of the present invention was added to and mixed with the above mixture in a mortar to produce a resin composition.
  • Part of the obtained resin composition was cast into a mold and cured at a temperature of 100°C and a pressure of 20 MPa for a retention time of 2 hours by using a thermal press device to produce a test sample having a diameter of 10 mm and a thickness of 1 mm, and the heat conductivity of the test sample was measured by a laser flash method using a laser flash thermoproperty measuring instrument (LFA-502 of Kyoto Electronics Manufacturing Co., Ltd.).
  • Example 1 An aluminum nitride powder was obtained in the same manner as in Example 1 except that the raw material composition in Example 1 was changed as shown in Table 1.
  • Example 1 An aluminum nitride powder was obtained in the same manner as in Example 1 except that the raw material composition in Example 1 was changed as shown in Table 1.
  • a molded body was produced in the same manner as in Example 6 except that 633 parts by weight of an aluminum nitride powder containing 70 vol% of spherical aluminum nitride (made of Tokuyama Corporation) having an average particle diameter of 22 ⁇ m based on 100 parts by weight of a resin used in Example 6 and measured for heat conductivity and insulation breakdown voltage. The results are shown in Table 3.
  • the aluminum nitride particle of the present invention has a large particle diameter and such a characteristic form that it has a hexagonal columnar barrel part and bowl-like projection parts at both ends of the columnar part as described above.
  • this particle is filled into a resin as a filler, the chances of surface contact between aluminum nitride particles grow due to the above hexagonal columnar planes, thereby making it possible to improve the heat conductivity of the above molded body as compared with conventional spherical particles.
  • the above aluminum nitride particle has a ratio of long diameter to short diameter close to that of a sphere, it has high flowability and exhibits high kneadability with a resin.
  • a particle having at least one flat face on the projection parts as a preferred example can further improve heat conductivity.
  • Voids are hardly formed in the aluminum nitride particle of the present invention due to its production method, and an aluminum nitride particle having 5 or less voids having a diameter of 2 ⁇ m or more existent therein as a preferred example can provide high insulation resistance strength to a resin obtained by filling the particle.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Ceramic Products (AREA)

Claims (9)

  1. Aluminiumnitridpartikel mit einem hexagonalen säulenförmigen Zylinderteil und schüsselartigen vorstehenden Teilen an beiden Enden des säulenförmigen Teils, wobei der lange Durchmesser (D) des Zylinderteils 10 bis 250 µm beträgt, das Verhältnis (L1/D) des Abstands (L1) zwischen den Spitzen der beiden vorstehenden Teile zu dem langen Durchmesser (D) des Zylinderteils 0,7 bis 1,3 beträgt und der Prozentsatz der Länge oder Dicke (L2) des Zylinderteils zu dem Abstand (L1) zwischen den Spitzen der beiden vorstehenden Teile 10 bis 60 % beträgt.
  2. Aluminiumnitridpartikel nach Anspruch 1, wobei ein Teil jedes der vorstehenden Teile flach ist.
  3. Aluminiumnitridpartikel nach Anspruch 1 oder 2, wobei die Anzahl der Hohlräume, die in dem Aluminiumnitridpartikel vorhanden sind und einen Durchmesser von 2 µm oder mehr haben, für jedes Partikel 5 oder weniger beträgt.
  4. Aluminiumnitridpulver, das nicht weniger als 40 Vol.-% des Aluminiumnitridpartikels nach einem der Ansprüche 1 bis 3 enthält.
  5. Harzzusammensetzung, umfassend das Aluminiumnitridpartikel nach einem der Ansprüche 1 bis 3 und ein Harz, wobei die Menge des Aluminiumnitridpartikels in der Harzzusammensetzung 300 bis 1.000 Gewichtsteile, basierend auf 100 Gewichtsteilen des Harzes, beträgt.
  6. Harzzusammensetzung nach Anspruch 5, wobei das Harz ein thermoplastisches Harz oder wärmehärtbares Harz ist.
  7. Formkörper, gebildet aus der Harzzusammensetzung nach Anspruch 5 oder 6.
  8. Verfahren zur Herstellung eines Aluminiumnitridpulvers, das das Aluminiumnitridpartikel nach einem der Ansprüche 1 bis 3 umfasst, wobei das Verfahren das Erhitzen einer Rohmaterialmischung, die ein Aluminiumoxidpulver, ein Kohlenstoffpulver und eine Schwefelkomponente enthält, in einer Stickstoffgasatmosphäre umfasst, um das Aluminiumoxidpulver zu reduzieren und zu nitrieren, wobei die Carbo-thermische Reduktions-Nitrierung mit einer Nitrierungsrate von mindestens 3 bis 50 % unter Verwendung eines Mischgases aus 85 bis 55 Vol.-% eines Stickstoffgases und 15 bis 45 Vol.-% eines Verdünnungsgases als die Stickstoffgasatmosphäre durchgeführt wird und nach dem Ende der Carbo-thermischen Reduktions-Nitrierung eine Temperatur, die die Heiztemperatur für die Carbo-thermische Reduktions-Nitrierung ±30°C ist, für 10 Stunden oder mehr in einer Atmosphäre gehalten wird, in der das gebildete Aluminiumnitridpulver nicht oxidiert wird.
  9. Verfahren zur Herstellung eines Aluminiumnitridpulvers nach Anspruch 8, wobei die Menge der Schwefelkomponente 1,0 bis 20 Gewichtsteile, basierend auf 100 Gewichtsteilen des Aluminiumoxidpulvers, beträgt.
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WO2018173170A1 (ja) * 2017-03-22 2018-09-27 日本碍子株式会社 窒化アルミニウム粒子
JP7129892B2 (ja) * 2018-11-29 2022-09-02 株式会社トクヤマ 窒化アルミニウム粉末
JP7233264B2 (ja) * 2019-03-15 2023-03-06 株式会社トクヤマ 複合フィラーおよび樹脂組成物
WO2020195776A1 (ja) 2019-03-22 2020-10-01 株式会社トクヤマ 窒化アルミニウム粒子
JP7292941B2 (ja) * 2019-04-19 2023-06-19 株式会社トクヤマ 窒化アルミニウム複合フィラー
JP7257866B2 (ja) * 2019-04-25 2023-04-14 株式会社トクヤマ 複合フィラー
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JPWO2017131239A1 (ja) 2018-11-22
KR20180109863A (ko) 2018-10-08
EP3409643A1 (de) 2018-12-05
JP6737819B2 (ja) 2020-08-12
TW201738173A (zh) 2017-11-01
EP3409643A4 (de) 2019-10-30
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US20190031510A1 (en) 2019-01-31
CN108290736A (zh) 2018-07-17

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